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Thesecondlawleadstothedefinitionofanewpropertycalledentropy.
TheClausiusInequality
Thefirstlawissimplyanenergybalance.However,thesecondlawleadstoaninequality;
an irreversible process is less efficient than a reversible process. Another important
inequalityinthermodynamicsistheClausiusinequality:
Q
T
Thatis,thecyclicintegralofQ/Tisalwayslessthanorequaltozero.Thisisvalidforall
cycles,reversibleorirreversible.
Forinternallyreversiblecycles,itcanbeshownthat:
Q
T
0
int, rev
Entropy
TheClausiusinequalityformsthebasisforthedefinitionofanewpropertycalledentropy.
As can be seen in the equation above, for an internally reversible process the cyclic
integralofQ/Tiszero.Aquantitywhosecyclicintegraliszerodependsonthestateonly
andnottheprocesspath,andthusitisaproperty.
Clausiusin1865realizedthathediscoveredanewpropertyandhecalleditentropy:
Q
dS
T int,rev
(kJ/K)
Entropyperunitmassisdesignatedbys(kJ/kg.K).
Theentropychangeofasystemduringaprocesscanbecalculated:
Q
S S 2 S1
T int, rev
1
2
(kJ/K)
To perform this integral, one needs to know the relation between Q and T during the
process.
Note that the cyclic integral of Q / T will give us the entropy change only if the
integrationcarriedoutalonganinternallyreversiblepathbetweentwostates.
Forirreversibleprocesses,wemayimagineareversibleprocessbetweenthetwostates
(initialandfinal)andcalculatetheentropychange(sinceentropyisaproperty).
M.BahramiENSC388(F09)Entropy1
TheIncreaseofEntropyPrinciple
Entropy change of a closed system during an irreversible process is greater that the
integralofQ/Tevaluatedfortheprocess.Inthelimitingcaseofareversibleprocess,
theybecomeequal.
dS
Q
T
Theentropygeneratedduringaprocessiscalledentropygeneration,andisdenotedby
Sgen,
2
S S 2 S1
S gen
Note that the entropy generation Sgen is always a positive quantity or zero (reversible
process).Itsvaluedependsontheprocess,thusitisnotapropertyofasystem.
The entropy of an isolated system during a process always increases, or in the limiting
caseofareversibleprocessremainsconstant(itnever decreases). This isknownasthe
increaseofentropyprinciple.
The entropy change of a system or its surroundings can be negative; but entropy
generationcannot.
S gen
0
0
irreversible process
reversible process
impossible process
1 A process must proceeds in the direction that complies with the increase of entropy
principle,Sgen>0.Aprocessthatviolatesthisprincipleisimpossible.
2Entropyisanonconservedproperty,andthereisnosuchthingastheconservationof
entropy.Therefore,theentropyofuniverseiscontinuouslyincreasing.
3Theperformanceofengineeringsystemsisdegradedbythepresenceofirreversibility.
The entropy generation is a measure of the magnitudes of the irreversibilities present
duringtheprocess.
EntropyBalance
Entropyisameasureofmoleculardisorderorrandomnessofasystem,andthesecond
lawstatesthatentropycanbecreatedbutitcannotbedestroyed.
Theincreaseofentropyprincipleisexpressedas
Entropychange=Entropytransfer+Entropygeneration
EntropyChange
Theentropybalanceiseasiertoapplythatenergybalance,sinceunlikeenergy(whichhas
manyformssuchasheatandwork)entropyhasonlyoneform.Theentropychangefora
systemduringaprocessis:
Entropychange=EntropyatfinalstateEntropyatinitialstate
MechanismsofEntropyTransfer
Entropycanbetransferredtoorfromasystemintwoforms:heattransferandmassflow.
Thus,theentropytransferforanadiabaticclosedsystemiszero.
HeatTransfer:heatisaformofdisorganizedenergyandsomedisorganization(entropy)
willflowwithheat.Heatrejectionistheonlywaythattheentropyofafixedmasscanbe
decreased. The ratio of the heat transfer Q/ T (absolute temperature) at a location is
calledentropyfloworentropytransfer
Entropy transfer with heat (T const.)
S heat
SinceT(inKelvin)isalwayspositive,thedirectionofentropytransferisthesameofthe
directionofheattransfer.
Whentwosystemsareincontact,theentropytransferfromwarmersystemisequalto
the entropy transfer to the colder system since the boundary has no thickness and
occupiesnovolume.
Notethatworkisentropyfree,andnoentropyistransferredwithwork.
MassFlow:masscontainsentropyaswellasenergy,bothentropyandenergycontentsof
asystemareproportionaltothemass.Whenamassintheamountofmentersorleaves
asystem,entropyintheamountofms(sisthespecificentropy)accompaniesit.
EntropyBalanceforaClosedSystem
Aclosedsystemincludesnomassflowacrossitsboundaries,andtheentropychangeis
simplythedifferencebetweentheinitialandfinalentropiesofthesystem.
Theentropychangeofaclosedsystemisduetotheentropytransferaccompanyingheat
transferandtheentropygenerationwithinthesystemboundaries:
Entropychangeofthesystem=Entropytransferwithheat+Entropygeneration
M.BahramiENSC388(F09)Entropy3
S 2 S1
Qk
S gen
Tk
Therefore,foranadiabaticclosedsystem,wehave:
Sadiabatic=Sgen
ForaninternallyreversibleadiabaticprocessS=0,becauseSgen=0.
Thetotalentropygeneratedduringaprocesscanbedeterminedbyapplyingtheentropy
balance to an extended system that includes both the system and its immediate
surroundingswhereexternalirreversibilitymightbeoccurring.
Example1:Entropybalanceforaclosedsystem
Saturated liquid water at 100 C is contained in a pistoncylinder assembly. The water
undergoesaprocesstothecorrespondingsaturatedvaporstate,duringwhichthepiston
movesfreelyinthecylinder.Thereisnoheattransferwiththesurroundings.Ifthechange
ofstateisbroughtaboutbytheactionofapaddlewheel,determinethenetworkperunit
mass,inkJ/kg,andtheamountofentropyproducedperunitmass,inkJ/kg.K.
Insulated
Water
Paddlewheel
Assumptions:
1Thewaterinthepistoncylinderassemblyisaclosedsystem.
2Thereisnoheattransferwiththesurroundings.
3Thesystemisatanequilibriumstateinitiallyandfinally.PE=KE=0.
Solution
Thenetworkcanbecalculatedbyusingthelaw:
U+KE+PE=QW
Thatissimplifiesto:U=W
M.BahramiENSC388(F09)Entropy4
Onaunitmassbasis,theenergybalancebecomes:
W/m=(uguf)
FromTableA4,
W/m=2087.6kJ/kg
The negative sign indicates that the work input by the stirring is greater than the work
donebythewaterasitexpands.
Usinganentropybalance,theamountofentropyproducedcanbefound.Sincethereis
noheattransfer,
Q
S
S gen S gen
T
Onaunitmassbasis,thisbecomes:
Sgen/m=sgsf
UsingTableA4
Sgen/m=6.048kJ/kg.K
EntropyBalanceforaControlVolume
In addition to methods discussed for closed system, the entropy can be exchanged
throughmassflowsacrosstheboundariesofthecontrolvolume.
mi
Control
volume
si
mo
T
se
Theentropybalanceintherateformforacontrolvolumebecomes:
dS CV
Q
k mi s i me s e S gen
,CV
dt
Tk
Forasteadystatesteadyflowprocess,itsimplifiesto:
S gen
,CV m e s e mi s i
Qk
Tk
M.BahramiENSC388(F09)Entropy5
Example2:EntropybalanceforaCV
Steamentersaturbinewithapressureof3MPa,atemperatureof400C,andavelocity
of160m/s.Saturatedvaporat100Cexitswithavelocityof100m/s.Atsteadystate,the
turbine develops work equal to 540 kJ/kg. Heat transfer between the turbine and its
surroundingsoccuratanaverageoutersurfacetemperatureof350K.Determinetherate
at which entropy is produced within the turbine per kg of steam flowing, in kJ/kg.K.
Neglectthechangeinpotentialenergybetweeninletandexit.
Assumptions:
1SteadystateoperationinCV.PE=0.
2Turbineoutersurfaceisataspecifiedaveragetemperature.
P1=3MPa
T1=400C
W/m=540kJ/kg
V1=160m/s
Turbine
T2=100C
V2=100m/s
Tb=350K
Sat.vapor
Fromthemassbalance,weknowthatm=m1=m2
Sincetheprocessissteadystate,onecanwrite:
Qk
m ( si s e ) S gen
,CV
Tk
TheheattransferoccursatTb=350K,thefirsttermoftherighthandsideoftheentropy
balancereducestoQ/Tb
S gen
,CV
Qk
( s 2 s1 )
m Tk
Weneedtocalculatetherateofheattransfer.Thefirstlaw(energybalance)canbeused
tofindtheheattransferrate.Combiningthemassbalanceandthefirstlaw,onefinds:
V22 V12
QCV
WCV
h
h
2
1
2
m
m
M.BahramiENSC388(F09)Entropy6
FromTableA6,h1=3230.9kJ/kg,andFromA4h2=2676.1kJ/kg.Aftersubstitution,and
convertingtheunits,onefinds:
QCV
22.6 kJ / kg
m
From Table A4, s2 = 7.3549 kJ/kg.K and from Table A6, s1 = 6.9212 kJ/kg.K. Inserting
valuesintotheexpressionforentropyproduction:
S gen
,CV
Q
k ( s 2 s1 ) 0.4983 kJ / kg.K
m Tk
Entropy
Entropycanbeviewedasameasureofmoleculardisorder,ormolecularrandomness.As
a system becomes more disordered, the positions of the molecules become less
predictableandtheentropyincreases.
Entropy
kJ/(kg.K)
Gas
Liquid
Solid
Fig.1:Entropyofasubstance(levelofdisorder)increaseswhenitmeltsfromsolidphase
toliquid.Ssolid<Sliquid<Sgas
Someremarks:
Work is an organized form of energy, free of disorder or randomness, thus free of
entropy.Therefore,thereisnoentropyassociatedwithenergytransferaswork.
The quantity of energy is always preserved during an actual process, based on the first
law,butthequalityisboundtodecrease(thesecondlaw).
Processes can occur only in the direction of increased overall entropy or molecular
disorder.Thus,theentireuniverseisgettingmoreandmorechaoticeveryday.
Atabsolutezero(0K),moleculesbecomecompletelymotionless,thisrepresentsastateof
ultimate molecular order (and minimum energy). Therefore, the entropy of a pure
M.BahramiENSC388(F09)Entropy7
crystallinesubstanceatzerotemperatureiszero.Thatisbecause;thereisnouncertainty
about the state of the molecules at that instant. This statement is the third law of
thermodynamics.
Sincethereisareferenceforentropy(absolutezero),entropyisanabsoluteproperty.The
entropymeasuredwithrespecttoabsolutezeroiscalledabsoluteentropy.
The two diagrams used most extensively in the secondlaw analysis are the Ts and hs
diagrams.Foraninternallyreversibleprocess,onecanwrite:
Qint,rev Tds
(kJ)
T
Internally
reversible
process
Q=Tds
Fig.2:OnaTsdiagram,theareaunderaninternallyreversibleprocesspresentstheheat
transferfortheprocess.
Foraninternallyreversibleisothermalprocess,wehave:
Qint,rev=T0ds
In a Ts diagram, an isentropic process is represented by a vertical line. An isentropic
processisaprocessinwhichentropyremainsconstant.Asaresultanisentropicprocess
involvesnoheattransfer.Therefore:
Isentropicprocess(s2=s1)=Reversible+Adiabatic
EvaluationofEntropyChange
Thedifferentialformoftheconservationofenergyforaclosedsystem(fixedmass)foran
internallyreversibleprocessis:
Qint,revWint,rev=dU
where,
Qint,rev=TdS
Wint,rev=PdV
Thus,
M.BahramiENSC388(F09)Entropy8
TdS=dU+PdV
or,perunitmass
Tds=du+Pdv
ThisiscalledthefirstGibbsequation.
Fromthedefinitionofenthalpy,h=u+Pv,onecanfind:
h=u+Pvdh=du+Pdv+vdP
EliminatingdufromthefirstGibbsequation,onefindsthesecondGibbsequation:
Tds=dhvdP
Explicit relations for differential changes in entropy can be obtained from Gibbs
equations:
du Pdv
T
T
dh vdP
ds
T
T
ds
Tocalculatetheentropychange,wemustknowtherelationshipbetweenduordhand
temperature.
CalculationoftheEntropyforSaturatedMixture
UseTablesA4andA5tofindsf,sgand/orsfgforthefollowing:
s=(1x)sf+xsgors=sf+xsfg
CalculationoftheEntropyforSuperheatedVapor
Giventwopropertiesorthestate,suchastemperatureandpressure,useTableA6.
CalculationoftheEntropyforCompressedLiquid
Intheabsenceofcompressedliquiddataforapropertyssf@T
EntropyChangeofSolidsandLiquids
Solids and liquids can be assumed as incompressible substances since their volumes
remainsessentiallyconstantduringaprocess.Thus,thefirstGibbsequationbecomes:
ds
du cdT
T
T
2
dT
s2 s1 c(T )
T
1
Assuminganaveragedvalueforspecificheat,oneobtains:
M.BahramiENSC388(F09)Entropy9
s2 s1 cave ln
T2
T1
EntropyChangeofIdealGas
Theentropychange of anidealgascanbe obtained, bysubstitutingdu=cvdTandP=
RT/vintoGibbsequation.
dT
dv
R
T
v
2
dT
v2
s2 s1 cv (T )
R ln
T
v1
1
ds cv
Assumingaveragedvaluesforspecificheats,oneobtains:
T2
v
R ln 2
T1
v1
kJ
kg.K
T
P
s2 s1 c p , ave ln 2 R ln 2
T1
P1
kJ
kg.K
s2 s1 cv , ave ln
Forisentropicprocessesofidealgases,thefollowingrelationshipscanbefoundbysetting
ds=0,
ln
T2
R v2
ln
T1
C v v1
v
T
ln 2 ln 1
T1
v2
Cv
T2
T1
or
v1
v2
k 1
isentropic process
SinceR=cpcv,k=cp/cv,andthusR/cv=k1.
Inasimilarmanner,onefinds:
T2
T1
P2
P1
( k 1) / k
P2
P1
v1
v2
isentropic process
isentropic process
Theseequationscanbeexpressedinthefollowingcompactforms:
Tvk1=constant
TP(1k)/k=constant
M.BahramiENSC388(F09)Entropy10
Pvk=constant
Thespecificratiok,varieswithtemperature,andinisentropicrelationsaboveanaverage
kvalueshouldbeused.
Example3:Isentropicprocessofidealgas
A rigid, wellinsulated tank is filled initially with 5 kg of air at pressure 500 kPa and a
temperature500K.Aleakdevelops,andairslowlyescapesuntilthepressureoftheair
remaining in the tank is 100 kPa. Using the ideal gas model, determine the amount of
massremaininginthetankanditstemperature.
Slowleak
Insulatedtank
Assumptions:
1Asshowninthefigure,theclosedsystemisthemassinitiallyinthetankthatremainsin
thetank.
2Thereisnosignificantheattransferbetweenthesystemanditssurroundings.
3Irreversibilitieswithinthetankcanbeignoredastheairslowlyescapes.
Solutions:
Usingtheidealgasequationofstate,themassinitiallyinthetankthatremainsinthetank
attheendofprocessis:
P2V
P
RT2
m2 2
PV
P1
m1 1
RT1
m2
T1
T2
m1
SincethevolumeofthetankVremainsconstantduringtheprocess.Weneedtofindthe
final temperature T2. For the closed system under consideration (m1), there are no
irreversibilities,andnoheattransfer.Accordingly,itisanisentropicprocess,andthusthe
isentropicrelationshipscanbeused:
T2 P2
T1 P1
k 1 / k
P
T2 T1 2
P1
k 1 / k
M.BahramiENSC388(F09)Entropy11
Withaconstantk=1.4forair,aftersubstitutingvalues,onefinds:
T2=315.55K
Finally,insertingvaluesintotheexpressionforsystemmass
m2=(100/500)(500/315.55)(5kg)=1.58kg
ReversibleSteadyFlowWork
The conservation of energy equation for a steadyflow device undergoing an internally
reversibleprocesscanbeexpressedindifferentialformas
But
q rev Tds
q rev dh vdP
Tds dh vdP
Substitutingintotherelationabove,aftercancelingdh,ityields,
wrev=vdP+dke+dpe
Integrating,wefind
2
wrev vdP ke pe
(kJ / kg )
wrev vdP
(kJ / kg )
Fromtheaboveequationcanbeseenthat,thelargerthespecificvolumethelargerthe
reversible produced or consumed work by the steadyflow device. Thus, every effort
should be made to keep the specific volume of the flow as small as possible during a
compressionprocesstominimizetheinputwork.
When the fluid is incompressible, the specific volume remains constant during the
process,thustheaboveequationbecomes:
wrev=v(P1P2)kepe(kJ/kg)
For a steadystate flow of a liquid through a device that involves no work interactions
(suchasnozzleorapipesection),theworktermiszero,
vP2 P1
V22 V12
g z 2 z1 0
2
ThisisknownasBernoulliequationinfluidmechanics.
M.BahramiENSC388(F09)Entropy12